Tris(hydroxymethyl) acrylamidomethane polmer, inverse latex and microlatex containing same, use of said polymer, inverse latex and microlatex

ABSTRACT

The invention concerns a linear or crosslinked polymer, characterized in that it is obtainable either by copolymerizing N-[2-hydroxy-1,1-bis(hydroxymethyl)-ethyl]-propenamide, or by copolymerizing N-[2-hydroxy-1,1-bis(hydroxymethyl)ethyl][-propenamide with one or several monomers selected among cationic monomers, monomers comprising at least a strong acid function, partly salified or completely salified, monomers comprising at least a weak acid function, partly salified or completely salified or neutral monomers. The invention also concerns inverse latex or microlatex containing such a polymer. The invention further concerns the uses of said polymer in cosmetic or pharmaceutical compositions, as thickening agents in industrial or household detergents, as additives for assisted recovery of oil, as rheology modifier for drilling fluid or as flocculants for water treatment.

The present patent application relates to novel polymers, towater-in-oil inverse latexes and water-in-oil inverse microlatexescomprising them, to their process of preparation and to their use asflocculating, superabsorbing or rheology-modifying thickening agent.

During studies into the development of novel flocculating orsuperabsorbing thickening agents having a prolonged stability over time,the Applicant Company became interested in polymers ofN-[2-hydroxy-1,1-bis-(hydroxymethyl)ethyl]propenamide, also known astris-(hydroxymethyl)acrylamidomethane or THAM:

THAM is disclosed in the European patent application published under thenumber EP 0 900 786.

According to a first aspect of the present invention, a subject matterof the latter is a linear or crosslinked polymer, characterized in thatit is capable of being obtained either by homopolymerization ofN-[2-hydroxy-1, 1-bis(hydroxymethyl)ethyl]propenamide or bycopolymerization ofN-[2-hydroxy-1,1-bis(hydroxy-methyl)ethyl]propenamide with one or moremonomers chosen from cationic monomers, monomers comprising at leastone, partially salified or completely salified, strong acid functionalgroup, monomers comprising at least one, partially salified orcompletely salified, weak acid functional group, or neutral monomers.

The term “crosslinked polymer” denotes a nonlinear polymer which existsin the form of a three-dimensional network which is insoluble in waterbut which can swell in water and which thus results in the production ofa chemical gel.

The term “salified” denotes, for the strong or weak acid functionalgroups, the alkali metal salts, such as the sodium salt or the potassiumsalt, or the nitrogenous base salts, such as, for example, the ammoniumsalt or the monoethanolamine (HO—CH₂—CH₂—NH₃ ⁺) salt.

The term “copolymerization” means that the polymerization reactionemploys at the two different monomers. It can in particular employ threeor more than three different monomers.

When the polymerization reaction resulting in the copolymer which is asubject matter of the present invention employs one or more monomerscomprising a strong acid functional group, it is generally the sulfonicacid functional group or the phosphonic acid functional group, saidfunctional groups being partially or completely salified. Said monomercan, for example, be styrenesulfonic acid, 2-sulfoethyl methacrylate,styrenephosphonic acid, partially or completely salified, or,preferably, 2-methyl-2-[1-oxo-2-propenyl)amino]-1-propanesulfonic acid,partially or completely salified in the form of an alkali metal salt,such as, for example, the sodium salt or the potassium salt, of theammonium salt, of a salt of an amino alcohol, such as, for example, themonoethanol-amine salt, or of an amino acid salt, such as, for example,the lysine salt.

When the polymerization reaction resulting in the copolymer which is asubject matter of the present invention employs one or more monomerscomprising a weak acid functional group, it is generally the carboxylicacid functional group; said monomers are chosen more particularly fromacrylic acid, methacrylic acid, itaconic acid, maleic acid, partially orcompletely salified, or 3-methyl-3-[(1-oxo-2-propenyl)amino]butanoicacid, partially salified or completely salified.

When the polymerization reaction resulting in the copolymer which is asubject matter of the present invention employs one or more neutralmonomers, they are chosen more particularly from acrylamide,methacrylamide, vinylpyrrolidone, diacetone acrylamide, 2-hydroxyethylacrylate, 2,3-dihydroxypropyl acrylate, 2-hydroxyethyl methacrylate,2,3-dihydroxypropyl methacrylate or an ethoxylated derivative, with amolecular weight of between 400 and 1000, of each of these esters.

When the polymerization reaction resulting in the copolymer which is thesubject matter of the present invention employs one or more cationicmonomers, they are more particularly monomers comprising one or moreammonium groups or aminated precursors of these monomers; such as, forexample, 2, N,N,N-tetramethyl-2-[(1-oxo-2-propenyl)amino]propanammoniumchloride (AMPTAC), 2,N,N-trimethyl-2-[(1-oxo-2-propenyl)amino]propanammonium chloride,N,N,N-tri-methyl-3-[(1-oxo-2-propenyl)amino]propanammonium chloride(APTAC), diallyldimethylammonium chloride (DADMAC),N,N,N-trimethyl-2-[(1-oxo-2-propenyl)]ethan-ammonium chloride,N,N,N-trimethyl-2-[(1-oxo-2-methyl-2-propenyl)]ethanammonium chloride,N-[2-(dimethyl-amino)-1,1-dimethyl]acrylamide,N-[2-(methylamino)-1,1-dimethyl]acrylamide, 2-(dimethylamino)ethylacrylate, 2-(dimethylamino)ethyl methacrylate orN-[3-(dimethyl-amino)propyl]acrylamide.

A subject matter of the invention is more particularly the followingpolymers:

homopolymers of THAM, copolymers of THAM and of2-methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid, partiallyor completely salified in the sodium salt or ammonium salt form,copolymers of THAM and of acrylic acid, partially salified in the sodiumsalt or ammonium salt form, copolymers of THAM and of methacrylic acid,partially salified in the sodium salt or ammonium salt form, terpolymersof THAM, of acrylic acid and of acrylamide, partially salified in thesodium salt or ammonium salt form, copolymers of THAM and of2-methyl-2-[(1-oxo-2-propenyl)amino]-1-propane-sulfonic acid, partiallyor completely salified in the sodium salt or ammonium salt form,copolymers of THAM and of AMPTAC, copolymers of THAM and of APTAC,copolymers of THAM and of DADMAC, copolymers of THAM and of2-(dimethylamino)ethyl acrylate, copolymers of THAM and of2-(dimethylamino)ethyl methacrylate, terpolymers of THAM, of AMPTAC andof acrylamide, terpolymers of THAM, of AMPTAC and of diacetoneacrylamide, terpolymers of THAM, of APTAC and of acrylamide, terpolymersof THAM, of DADMAC and of diacetone acrylamide, terpolymers of THAM, of2-(dimethylamino)ethyl acrylate and of acrylamide or terpolymers ofTHAM, of 2-(dimethylamino)ethyl methacrylate and of diacetoneacrylamide.

According to a specific aspect of the present invention, the polymers asdefined above are linear polymers.

According to another specific aspect of the present invention, thepolymers as defined above are polymers crosslinked by a crosslinkingagent chosen from diethylene or polyethylene compounds and veryparticularly from diallyloxyacetic acid or one of the salts and inparticular its sodium salt, triallylamine, trimethylolpropanetriacrylate, ethylene glycol dimethacrylate, diethylene glycoldiacrylate, diallyl-urea or methylenebis(acrylamide). The crosslinkingagent is generally used in the molar proportion, expressed with respectto the monomers employed, of 0.005% to 1%, in particular of 0.01% to0.2% and more particularly of 0.01% to 0.1%.

The polymers as defined above have a molar proportion, expressed withrespect to the monomers employed, of THAM monomer generally of greaterthan or equal to 5%, more particularly of greater than or equal to 10%and very particularly of greater than or equal to 20%.

According to a second aspect of the present invention, a subject matterof the invention is a composition comprising an oil phase, an aqueousphase, at least one emulsifying agent of water-in-oil (W/O) type and atleast one emulsifying agent of oil-in-water (O/W) type, in the form of aself-invertible inverse latex comprising from 20% to 70% by weight andpreferably from 25% to 40% by weight of a polymer as defined above.

The inverse latex according to the invention generally comprises from2.5% to 15% by weight and preferably from 4% to 9% by weight ofemulsifying agents, among which agents from 20% to 50%, in particularfrom 25% to 40%, of the total weight of the emulsifying agents presentare of the water-in-oil (W/O) type and in which invention from 80% to50%, in particular from 75% to 60%, of the total weight of theemulsifying agents are of the oil-in-water (O/W) type.

In the inverse latex as defined above, the oil phase generallyrepresents from 15% to 50%, preferably from 20% to 25%, of its totalweight. The inverse latex comprises between 5% and 60% by weight ofwater and more particularly between 20% and 50% by weight of water. Thelatex according to the invention can also comprise various additives,such as complexing agents or chain-limiting agents.

According to a third aspect of the present invention, a subject matterof the invention is a composition comprising an oil phase, an aqueousphase, at least one emulsifying agent of water-in-oil (W/O) type and atleast one emulsifying agent of oil-in-water (O/W) type, in the form of aself-invertible inverse microlatex comprising from 10% to 50% by weightand preferably from 10% to 30% by weight of a polymer as defined above.

The inverse microlatex according to the invention generally comprisesfrom 5% to 10% by weight of a mixture of surfactants of W/O type and ofO/W type having an overall HLB number of greater than or equal to 9. Theoil phase generally represents from 15% to 50%, preferably from 20% to25%, of its total weight.

The term “emulsifying agent of the water-in-oil type” denotesemulsifying agents having an HLB value which is sufficiently low toprovide water-in-oil emulsions, such as the surface-active polymers soldunder the name of Hypermer™ or such as sorbitan esters, for example thesorbitan monooleate sold by Seppic under the name Montane™80, thesorbitan isostearate sold by Seppic under the name Montanem 70 or thesorbitan sesquioleate sold by Seppic under the name of Montane™ 83. Whena mixture of emulsifying agents of the water-in-oil type is concerned,the HLB value to be taken into consideration is that of said mixture.

The term “emulsifying agent of the oil-in-water type” emulsifying agentshaving an HLB value which is sufficiently high to provide oil-in-wateremulsions, such as, for example, ethoxylated sorbitan esters, such asthe ethoxylated sorbitan oleate comprising 20 mol of ethylene oxide, theethoxylated castor oil comprising 40 mol of ethylene oxide and theethoxylated sorbitan laurate comprising 20 mol of ethylene oxide, soldby Seppic under the names Montanox™ 80, Simulsol™ OL 50 and Montanox™ 20respectively, the ethoxylated lauryl alcohol comprising 7 mol ofethylene oxide sold by Seppic under the name Simulsolw™ P7, the ethylenedeca-ethoxylated oleyl/cetyl alcohol sold by Seppic under the nameSimulsol™ OC 710 or the polyethoxylated sorbitan hexaoleates sold byAtlas Chemical Industries under the names G-1086 and G-1096, ethoxylatednonyl-phenols or alkyl polyglucosides of formula (I):R₁—O-(G)_(x)-H   (I)such as Simulsol™ SL 8, sold by Seppic, which is an aqueous solutioncomprising between approximately 35% and 45% by weight of a mixture ofalkyl polyglucosides consisting of between 45% by weight and 55% byweight of a compound of formula (I) in which x is equal to approximately1.45 and R₁ represents a decyl radical and between 45% by weight and 55%by weight of a compound of formula (I) in which x is equal toapproximately 1.45 and R₁ represents an octyl radical; Simulsolw™ SL10,sold by Seppic, which is an aqueous solution comprising betweenapproximately 50% by weight and 60% by weight of a mixture of alkylpolyglucosides consisting of approximately 85% by weight of a compoundof formula (I) in which x is equal to approximately 1.45 and R₁represents a decyl radical, approximately 7.5% by weight of a compoundof formula (I) in which x is equal to approximately 1.45 and R₁represents a dodecyl radical and approximately 7.5% by weight of acompound of formula (I) in which x is equal to approximately 1.45 and R₁represents a tetradecyl radical; Simulsol™ SL11, sold by Seppic, whichis an aqueous solution comprising between approximately 50% by weightand 60% by weight of a mixture of alkyl polyglucosides of formula (I) inwhich x is equal to approximately 1.45 and R₁ represents an undecylradical, or Simulsol™ SL26, sold by Seppic, which is an aqueous solutioncomprising between approximately 50% by weight and 60% by weight of amixture of alkyl polyglucosides consisting of approximately 70% byweight of a compound of formula (I) in which x is equal to approximately1.45 and R₁ represents a dodecyl radical, approximately 25% by weight ofa compound of formula (I) in which x is equal to approximately 1.45 andR₁ represents a tetradecyl radical and approximately 5% by weight of acompound of formula (I) in which x is equal to approximately 1.45 and R₁represents a hexadecyl radical.

The oil phase of the inverse latex or of the inverse microlatexdescribed above is composed either:

of a commercial mineral oil comprising saturated hydrocarbons ofparaffin, isoparaffin or cycloparaffin type exhibiting, at ambienttemperature, a density between 0.7 and 0.9 and a boiling point ofgreater than 180° C., such as, for example, Isopar™ M, Isopar™ L,Isopar™E or Isopar™G, Exxol™ D 100 S, sold by Exxon, or white mineraloils in accordance with the FDA 21 CFR 172.878 and FR 178.3620(a)regulations, such as Marcol™ 52 or Marcol™82, also sold by Exxon;

or of hydrogenated polyisobutene, sold in France by Ets B. Rossow et Cieunder the name Parleam-Polysynlane™ and mentioned in Michael and IreneAsh; Thesaurus of Chemical Products, Chemical Publishing Co. Inc., 1986,Volume I, page 211 (ISBN 0 7131 3603 0);

or of isohexadecane, which is identified in Chemical Abstracts by thenumber RN=93685-80-4 and which is a mixture of C₁₂, C₁₆ and C₂₀isoparaffins comprising at least 97% of C₁₆ isoparaffins, among whichthe main constituent is 2,2,4,4,6,8,8-heptamethylnonane (RN=4390-04-9).It is sold in France by Bayer;

or of isododecane, sold in France by Bayer;

or of squalane, which is identified in Chemical Abstracts by the numberRN=111-01-3 and which is a mixture of hydrocarbons comprising more than80% by weight of 2,6,10,15,19,23-hexamethyltetracosane. It is sold inFrance by Sophim under the name Phytosqualane™;

or among the esters of fatty acids of formula (II):R₁—(C═O)—O—[[CH₂—CH[O—[C(═O)]_(m)—R₂]—CH₂—O]_(n)—[C(═O)]_(p)]_(q)—R₃  (II)in which R₁ represents a saturated or unsaturated and linear or branchedhydrocarbonaceous chain comprising from 7 to 30 carbon atoms, R₂represents, independently of R₁, a hydrogen atom or a saturated orunsaturated and linear or branched hydrocarbonaceous chain comprisingfrom 7 to 30 carbon atoms, R₃ represents, independently of R₁ or of R₂,a hydrogen atom or a saturated or unsaturated and linear or branchedhydrocarbonaceous chain comprising from 1 to 30 carbon atoms, and m, n,p and q are, independently of one another, equal to 0 or to 1, it beingunderstood that, when R₃ represents a hydrogen atom, q is other than 0.As compounds of formula (II), there are more particularly the compoundsof formula (IIa):R₁—(C═O)—O—CH₂—CH[O—[C (═O)]_(m)—R₂]—CH₂—O—[C(═O)]_(p)—R₃  (IIa)corresponding to the formula (II) as defined above in which q and n areequal to 1, or a mixture of compounds of formula (IIa); in this case,they are preferably either a compound of formula (IIa₁):R₁—(C═O)—O—CH₂—CH(OH)—CH₂—OH   (IIa₁)corresponding to the formula (IIa) as defined above in which m and p areequal to 0 and R₂ and R₃ represent a hydrogen atom, or a compound offormula (IIa₂):R₁—(C═O)—O—CH₂—CH(OH)—CH₂—O—C(═O)—R₃  (IIa₂)corresponding to the formula (IIa) as defined above in which p is equalto 1, m is equal to 0 and R₂ represents a hydrogen atom, or a compoundof formula (IIa₃):R₁—(C═O)—O—CH₂—CH[O—C(═O)—R₂]—CH₂—O—C(═O)—R₃  (IIa₃)corresponding to the formula (IIa) as defined above in which m and p areequal to 1, or a mixture of compounds of formulae (IIa₁), (IIa₂) and/or(IIa₃).

As examples of compounds of formulae (IIa₁), (IIa₂) or (IIa₃), thereare, for example, triglycerides of fatty acids or of mixtures of fattyacids, such as the mixture of triglycerides of fatty acids comprisingfrom 6 to 10 carbon atoms sold under the name Softenol™ 3819, themixture of triglycerides of fatty acids comprising from 8 to 10 carbonatoms sold under the name Softenol™ 3108, the mixture of triglyceridesof fatty acids comprising from 8 to 18 carbon atoms sold under the nameSoftenol™ 3178, the mixture of triglycerides of fatty acids comprisingfrom 12 to 18 carbon atoms sold under the name Softenol™ 3100, themixture of triglycerides of fatty acids comprising 7 carbon atoms soldunder the name Softenol™ 3107, the mixture of triglycerides of fattyacids comprising 14 carbon atoms sold under the name Softenol™ 3114 orthe mixture of triglycerides of fatty acids comprising 18 carbon atomssold under the name Softenol™ 3118, glyceryl dilaurate, glyceryldioleate, glyceryl isostearate, glyceryl distearate, glycerylmonolaurate, glyceryl monooleate, glyceryl monoisostearate, glycerylmonostearate or a mixture of these compounds.

According to another aspect of the present invention, another subjectmatter of the invention is a process for the preparation of the inverselatex as defined above, characterized in that:

a) an aqueous solution comprising the monomers and the optionaladditives is emulsified in an oily phase in the presence of one or moreemulsifying agents of water-in-oil type,

b) the polymerization reaction is initiated by introduction, into theemulsion formed in a), of a free-radical initiator and optionally of acoinitiator, and then the polymerization reaction is allowed to takeplace,

c) when the polymerization reaction is finished, one or more emulsifyingagents of oil-in-water type is/are introduced at a temperature of below50° C.

According to an alternative form of this process, the reaction mediumresulting from stage b) is concentrated by distillation before theimplementation of stage c).

According to a preferred implementation of the process as defined above,the polymerization reaction is initiated by a redox couple whichgenerates hydrogensulfite (HSO₃ ⁻) ions, such as the cumenehydro-peroxide/sodium metabisulfite (Na₂S₂O₅) couple or the cumenehydroperoxide/thionyl chloride (SOCl₂) couple, at a temperature of lessthan or equal to 10° C., if desired accompanied by an agent which is acoinitiator of polymerization, such as, for example,azobis(iso-butyronitrile), dilauryl peroxide or sodium persulfate, andis then carried out either quasiadiabatically, up to a temperature ofgreater than or equal to 50° C., or by controlling the temperature.

According to another aspect of the present invention, another subjectmatter of the invention is a process for the preparation of the inversemicrolatex as defined above, characterized in that:

a) an aqueous solution comprising the monomers and the optionaladditives is emulsified in an oil phase in the presence of one or moreemulsifying agents, so as to form a microemulsion,

b) the polymerization reaction is initiated by introduction, into theemulsion formed in a), of a free-radical initiator and optionally of acoinitiator, and then the polymerization reaction is allowed to takeplace.

The polymer as defined above can be isolated from the preceding inverselatex or from the preceding inverse microlatex by the various processesknown to a person skilled in the art, such as the precipitationtechnique, which consists in pouring the latex or the microlatex into alarge excess of solvent, such as acetone, isopropanol or ethanol, orsuch as the spray drying technique, which is disclosed in theinternational publication WO 00/01757.

The polymer, the inverse polymer latex or the inverse polymer microlatexwhich are subject matters of the present invention can be employed, forexample, as thickener for cosmetic or pharmaceutical compositions, asthickener for printing pastes for the textile industry, as thickenersfor industrial or household detergents, as additives for the assistedrecovery of oil, as rheology modifier for drilling muds or asflocculants for water treatment.

The following examples illustrate the present invention without,however, limiting it.

EXAMPLE A (COMPARATIVE) Inverse Emulsion of a Copolymer of Sodium2-methyl-2-[(1-oxo-2-propenyl)-amino]-1-propanesulfonate and ofAcrylamide (ATBS-AA)

Procedure

The following are charged to a beaker with stirring:

-   -   80 g of deionized water,    -   211.6 g of a 50% by weight aqueous acrylamide solution,    -   93 g of a 48% by weight aqueous sodium hydroxide solution,    -   308.4 g of        2-methyl-2-[(1-oxo-2-propenyl)-amino]-1-propanesulfonic acid        (sold in France by CIM Chemicals), and    -   0.47 g of a 40% by weight commercial sodium        diethylenetriaminepentaacetate solution.

At the same time, an organic phase is prepared by successivelyintroducing into a beaker, with stirring:

-   -   220 g of Isopar™ M,    -   27.5 g of Montane™ 80 VG (sorbitan monooleate sold by Seppic).

The aqueous phase is gradually introduced into the organic phase and isthen subjected to vigorous mechanical stirring of UltraTurrax™ type,this device being sold by Ika. The emulsion obtained is then transferredto a polymerization reactor and is subjected to extensive nitrogensparging to remove the oxygen. 5 ml of a 0.3% by weight solution ofcumene hydroperoxide in Isopar™ M are then introduced.

After the time sufficient for good homogenization of the solution, 25 mlof a 0.3% by weight aqueous sodium metabisulfite solution are introducedat the rate of 0.5 ml/minute, the temperature being allowed to riseuntil it stabilizes. The reaction medium is maintained at thistemperature for 90 minutes, the combination is then cooled toapproximately 30° C. and, finally, 50 g of Simulsol™ P7 (7 EOpolyethoxylated lauryl alcohol) are added in order to obtain the desiredemulsion.

Evaluation of the Properties of the Latex Obtained

Viscosity at 25° C. of the latex at 1% in water (Brookfield RVT, Spindle6, speed 5): η=11 200 mPa·s;

Viscosity at 25° C. of the latex at 1% in water+0.1% NaCl (BrookfieldRVT, Spindle 6, speed 5): η=6320 mPa·s.

EXAMPLE 1 (ACCORDING TO THE INVENTION) Inverse Emulsion of a Copolymerof Sodium 2-methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonate and ofN-[2-hydroxy-1,1-bis(hydroxymethyl)ethyl]propenamide (ATBS-THAM)

Procedure

The following are charged to a beaker with stirring:

-   -   356.2 g of deionized water,    -   221.4 g of a 55% by weight sodium        2-methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonate        solution,    -   100.5 g of        N-[2-hydroxy-1,1-bis(hydroxy-methyl)ethyl]propenamide, and    -   0.45 g of a 40% by weight commercial sodium        diethylenetriaminepentaacetate solution.

At the same time, an organic phase is prepared by successivelyintroducing into a beaker, with stirring:

-   -   218 g of Isopar™ M and    -   24.2 g of Montane™ 80 VG.

The aqueous phase is gradually introduced into the organic phase and isthen subjected to vigorous mechanical stirring of UltraTurrax™ type. Theemulsion obtained is then transferred to a polymerization reactor and issubjected to extensive nitrogen sparging to remove the oxygen. 5 ml of a0.3% by weight solution of cumene hydroperoxide in Isopar™ M are thenintroduced.

After the time sufficient for good homogenization of the solution, 25 mlof a 0.3% by weight aqueous sodium metabisulfite solution are introducedat the rate of 0.5 ml/minute, the temperature being allowed to riseuntil it stabilizes. The reaction medium is maintained at thistemperature for 90 minutes, the combination is then cooled toapproximately 30° C. and, finally, 50 g of Simulsol™ P7 are added inorder to obtain the desired emulsion.

Evaluation of the Properties of the Latex Obtained

Viscosity at 25° C. of the latex at 1% in water (Brookfield RVT, Spindle6, speed 5): η=52 600 mPa·s;

Viscosity at 25° C. of the latex at 1% in water+0.1% NaCl (BrookfieldRVT, Spindle 6, speed 5): η=18 000 mPa·s.

EXAMPLE B (COMPARATIVE) Inverse Emulsion of a Copolymer of Sodium2-methyl-2-[(1-oxo-2-propenyl)-amino]-1-propanesulfonate and ofAcrylamide Crosslinked with MBA (ATBS-AA)

Procedure

The following are charged to a beaker with stirring:

-   -   80 g of deionized water,    -   211.6 g of a 50% by weight aqueous acrylamide solution,    -   93 g of a 48% by weight aqueous sodium hydroxide solution,    -   308.4 g of        2-methyl-2-[(1-oxo-2-propenyl)-amino]-1-propanesulfonic acid        (sold in France by CIM Chemicals),    -   0.016 g of methylenebis(acrylamide) (MBA), and    -   0.47 g of a 40% by weight commercial sodium        diethylenetriaminepentaacetate solution.

At the same time, an organic phase is prepared by successivelyintroducing into a beaker, with stirring:

-   -   220 g of Isopar™ M,    -   27.5 g of Montane™ 80 VG.

The aqueous phase is gradually introduced into the organic phase and isthen subjected to vigorous mechanical stirring of UltraTurrax™ type. Theemulsion obtained is then transferred to a polymerization reactor and issubjected to extensive nitrogen sparging to remove the oxygen. 5 ml of a0.3% by weight solution of cumene hydroperoxide in Isopar™ M are thenintroduced.

After the time sufficient for good homogenization of the solution, 25 mlof a 0.3% by weight aqueous sodium metabisulfite solution are introducedat the rate of 0.5 ml/minute, the temperature being allowed to riseuntil it stabilizes. The reaction medium is maintained at thistemperature for 90 minutes, the combination is then cooled toapproximately 30° C. and, finally, 50 g of Simulsol™ P7 are added inorder to obtain the desired emulsion. Evaluation of the properties ofthe inverse latex obtained

Viscosity at 25° C. of the latex at 1% in water (Brookfield RVT, Spindle6, speed 5): η=40 000 mPa·s;

Viscosity at 25° C. of the latex at 1% in water+0.1% NaCl (BrookfieldRVT, Spindle 6, speed 5): η=7200 mPa·s.

EXAMPLE 2 (ACCORDING TO THE INVENTION) Inverse Emulsion of a Copolymerof Sodium 2-methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonate and ofN-[2-hydroxy-1,1-bis(hydroxymethyl)ethyl]propenamide Crosslinked withMBA (ATBS-TRAM)

Procedure

The following are charged to a beaker with stirring:

-   -   356.2 g of deionized water,    -   221.4 g of a 55% by weight sodium        2-methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonate        solution,    -   100.5 g of        N-[2-hydroxy-1,1-bis(hydroxy-methyl)ethyl]propenamide,    -   0.016 g of methylenebis(acrylamide) (MBA), and    -   0.45 g of a 40% by weight commercial sodium        diethylenetriaminepentaacetate solution.

At the same time, an organic phase is prepared by successivelyintroducing into a beaker, with stirring:

-   -   218 g of Isopar™ M and    -   24.2 g of Montane™ 80 VG.

The aqueous phase is gradually introduced into the organic phase and isthen subjected to vigorous mechanical stirring of UltraTurrax™ type. Theemulsion obtained is then transferred to a polymerization reactor and issubjected to extensive nitrogen sparging to remove the oxygen. 5 ml of a0.3% by weight solution of cumene hydroperoxide in Isopar™ M are thenintroduced.

After the time sufficient for good homogenization of the solution, 25 mlof a 0.3% by weight aqueous sodium metabisulfite solution are introducedat the rate of 0.5 ml/minute, the temperature being allowed to riseuntil it stabilizes. The reaction medium is maintained at thistemperature for 90 minutes, the combination is then cooled toapproximately 30° C. and, finally, 50 g of Simulsol™ P7 are added inorder to obtain the desired emulsion.

Evaluation of the Properties of the Latex Obtained

Viscosity at 25° C. of the latex at 1% in water (Brookfield RVT, Spindle6, speed 5): η=65 400 mPa·s;

Viscosity at 25° C. of the latex at 1% in water+0.1% NaCl (BrookfieldRVT, Spindle 6, speed 5): η=14 000 mPa·s.

EXAMPLE 3 (ACCORDING TO THE INVENTION) Inverse Micro-Emulsion of aCopolymer of Sodium2-methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonate andN-[2-hydroxy-1,1-bis(hydroxymethyl)ethyl]propenamide Crosslinked withMBA (ATBS-THAM)

Procedure

The following are charged to a beaker, with stirring:

-   -   114.8 g of deionized water,    -   67.2 g of a 55% by weight sodium        2-methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonate        solution,    -   30.5 g of N-[2-hydroxy-1,1-bis(hydroxy-methyl)ethyl]propenamide,        and    -   0.025 g of methylenebis(acrylamide) (MBA).

At the same time, an organic phase is prepared by successivelyintroducing into a beaker, with stirring:

-   -   212.5 g of Isopar™ M,    -   30.6 g of Montane™ 83 (sorbitan sesqui-oleate), and    -   45.4 g of Montanox™ 80 (20 EO polyethoxylated sorbitan oleate).

The aqueous phase is gradually introduced into the organic phase and isthen subjected to vigorous mechanical stirring of UltraTurrax™ type. Theemulsion obtained is then transferred to a polymerization reactor and issubjected to extensive nitrogen sparging to remove the oxygen. 5 ml of a0.3% by weight solution of cumene hydroperoxide in Isopar™ M are thenintroduced.

After the time sufficient for good homogenization of the solution, 25 mlof a 0.3% by weight aqueous sodium metabisulfite solution are introducedat the rate of 0.5 ml/minute, the temperature being allowed to riseuntil it stabilizes. The reaction medium is maintained at thistemperature for 90 minutes and then the combination is cooled toapproximately 30° C. in order to obtain the desired emulsion.

Evaluation of the Properties of the Microlatex Obtained

Viscosity at 25° C. of the latex at 1% in water (Brookfield RVT, Spindle6, speed 5): η=65 400 mPa·s;

Viscosity at 25° C. of the latex at 1% in water+0.1% NaCl (BrookfieldRVT, Spindle 6, speed 5): η=14 000 mPa·s.

Analysis of the Results

The viscosities, measured at 25° C. (Brookfield RVT, Spindle 6, speed 5;in mPa·s), are recorded in the following table; their comparison makesit possible to demonstrate that the improvement in the behavior towardsalt of the inverse latexes according to the invention is inherent tothe presence of THAM monomer in the polymer.

The comparison also reveals that, unexpectedly, en the uncrosslinkedTHAM polymers develop viscosity aqueous solution: Viscosity η of theViscosity η₁ of the latex at 1% in latex at 1% in water + Example No.water 0.1% NaCl A 11 200 6320 1 52 600 18 000 B 40 000 7200 2 65 400 14000 3 52 600 18 000

1-12. (canceled).
 13. A product polymer produced by the processcomprising: a) the homopolymerization ofN-[2-hydroxy-1,1-bis(hydroxy-methyl)ethyl]propenamide; or b) thecopolymerization of N-[2-hydroxy-1,1-bis(hydroxymethyl)ethyl]propenamidewith at least one or more monomers selected from the group consistingof: cationic monomers; monomers comprising at least one acid functionalgroup, wherein said acid group is partially or completely salified; andneutral monomers.
 14. The product of claim 13, wherein said productpolymer is linear or crosslinked.
 15. The product of claim 14, whereinthe crosslinking agent is diethylene or a polyethylene compound.
 16. Theproduct of claim 15, wherein said crosslinking agent is selected fromthe group consisting of: a) diallyloxyacetic acid; b) triallylamine; c)trimethylolpropane triacrylate; d) ethylene glycol dimethacrylate; e)diethylene glycol diacrylate; f diallylurea; and g)methylenebis(acrylamide).
 17. The product of claim 16, wherein saiddiallyloxyacetic acid, is salified in the form of its sodium salt.
 18. Acomposition comprising: a) a water phase component; b) an oil phasecomponent; c) at least one emulsifying agent of water-in-oil type; andd) at least one emulsifying agent of oil-in-water type, which is in theform of: i) a self-invertible inverse latex comprising from about 20% toabout 70% by weight of said product polymer of claim 13, or ii) aself-invertible inverse microlatex comprising from about 10% to about50% by weight of said product polymer of claim
 13. 19. The compositionof claim 18, wherein said latex comprises from about 25% to about 40% byweight of said product polymer.
 20. The composition of claim 19, whereinsaid microlatex comprises from about 10% to about 30% by weight of saidproduct polymer.
 21. The composition of claim 18, wherein said monomercomprising at least one acid functional group, which is strong, isselected from the group consisting of: a) styrenesulfonic acid; b)2-sulfoethyl methacrylate; and c) styrenephosphonic acid.
 22. Thecomposition of claim 21, wherein said strong acid functional group is2-methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid, whereinsaid acid is partially or completely salified in the form of at leastone salt selected from the group consisting of: a) an alkali metal salt;b) an ammonium salt, c) a salt of an amino alcohol; and d) an amino acidsalt.
 23. The composition of claim 18, wherein said monomer comprisingat least one acid functional group, which is weak, is selected from thegroup consisting of: a) acrylic acid; b) methacrylic acid; c) itaconicacid; and d) maleic acid.
 24. The composition of claim 23, wherein saidweak acid functional group is3-methyl-3-[(1-oxo-2-propenyl)amino]butanoic acid.
 25. The compositionof claim 18, wherein said neutral monomer is selected from the groupconsisting of: a) acrylamide; b) methacrylamide; c) vinylpyrrolidone; d)diacetone acrylamide; e) 2-hydroxyethyl acrylate; f) 2,3-dihydroxypropylacrylate; g) 2-hydroxyethyl methacrylate; and h) 2,3-dihydroxypropylmethacrylate or an ethoxylated derivative, wherein the esters each havea molecular weight of between about 400 and about 1,000.
 26. Thecomposition of claim 18, wherein the cationic monomer is selected fromthe group consisting of: a) 2,N,N,N-tetramethyl-2-[(1-oxo-2-propenyl)amino]propanammonium chloride(AMPTAC); b) 2, N,N-trimethyl-2-[(1-oxo-2-propenyl)amino]propanammoniumchloride; c) N,N,N-trimethyl-3-[(1-oxo-2-propenyl)amino]propanammoniumchloride (APTAC); d) diallyldimethylammonium chloride (DADMAC); e)N,N,N-trimethyl-2-[(1-oxo-2-propenyl)]ethanammonium chloride; f)N,N,N-trimethyl-2-[(1-oxo-2-methyl-2-propenyl)]ethanammonium chloride;g) N-[2-(dimethylamino)- 1,1-dimethyl]acrylamide; h)N-[2-(methylamino)-1,1-dimethyl]acrylamide; i) 2-(dimethylamino)ethylacrylate; j) 2-(dimethylamino)ethyl methacrylate; and k)N-[3-(dimethylamino)propyl]acrylamide.
 27. The composition of claim 18,wherein the product polymer is selected from the group consisting of: a)homopolymers of THAM; b) copolymers of THAM and of2-methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid, whereinsaid acid is partially or completely salified in the sodium salt orammonium salt form; c) copolymers of THAM and of acrylic acid, whereinsaid acid is partially salified in the sodium salt or ammonium saltform; d) copolymers of THAM and of methacrylic acid, wherein said acidis partially salified in the sodium salt or ammonium salt form; e)terpolymers of THAM, of acrylic acid, and of acrylamide, wherein saidacid is partially salified in the sodium salt or ammonium salt form; f)copolymers of THAM and of2-methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid, whereinsaid acid is partially or completely salified in the sodium salt orammonium salt form; g) copolymers of THAM and of AMPTAC; h) copolymersof THAM and of APTAC; i) copolymers of THAM and of DADMAC; j) copolymersof THAM and of 2-(dimethylamino)ethyl acrylate; k) copolymers of THAMand of 2-(dimethylamino)ethyl methacrylate; l) terpolymers of THAM, ofAMPTAC, and of acrylamide; m) terpolymers of THAM, of AMPTAC, and ofdiacetone acrylamide; n) terpolymers of THAM, of APTAC, and ofacrylamide; o) terpolymers of THAM, of DADMAC, and of diacetoneacrylamide; p) terpolymers of THAM, of 2-(dimethylamino)ethyl acrylate,and of acrylamide; and q) terpolymers of THAM, of 2-(dimethylamino)ethylmethacrylate, and of diacetone acrylamide.
 28. The composition of claim27, wherein the molar proportion of the THAM monomer, expressed withrespect to the total amount of monomers employed, is greater than orequal to 5%.
 29. The composition of claim 28, wherein the molarproportion is greater than or equal to 10%.
 30. The composition of claim29, wherein the molar proportion is greater than or equal to 20%.
 31. Aprocess for the preparation of the inverse latex of claim 18,comprising: a) preparing an aqueous solution comprising the monomers andthe optional additives, wherein said solution is emulsified in an oilyphase in the presence of one or more emulsifying agents of water-in-oiltype, to produce an emulsion; b) initiating a polymerization reaction byintroducing, into said emulsion, a free-radical initiator, andoptionally a coinitiator, wherein the polymerization reaction proceeds;and c) introducing upon completion of the polymerization reaction, atleast one emulsifying agent of oil-in-water type at a temperature ofbelow 50° C.
 32. A process for the preparation of the inverse microlatexof claim 18, wherein: a) preparing an aqueous solution comprising themonomers and the optional additives, wherein said solution is emulsifiedin an oily phase in the presence of one or more emulsifying agents, soas to form a microemulsion; and b) initiating a polymerization reactionby introducing, into said microemulsion, a free-radical initiator, andoptionally a coinitiator.
 33. The composition of clam 18, wherein saidcomposition is utilized as a thickener in: a) cosmetic or pharmaceuticalcompositions; b) printing paste for the textile industry; or c)industrial or household detergents.
 34. The composition of clam 18,wherein said composition is utilized as an additive in the assistedrecovery of oil.
 35. The composition of clam 18, wherein saidcomposition is utilized as a rheology modifier in drilling mudoperations.
 36. The composition of clam 18, wherein said composition isutilized as a flocculant in a water treatment process.